CN113880219A - Method for degrading organic dye wastewater through photo-assisted carbide slag ferrosilicon catalysis - Google Patents
Method for degrading organic dye wastewater through photo-assisted carbide slag ferrosilicon catalysis Download PDFInfo
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- CN113880219A CN113880219A CN202111253024.4A CN202111253024A CN113880219A CN 113880219 A CN113880219 A CN 113880219A CN 202111253024 A CN202111253024 A CN 202111253024A CN 113880219 A CN113880219 A CN 113880219A
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- ferrosilicon
- organic dye
- carbide slag
- dye wastewater
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention relates to the technical field of water treatment and solid waste treatment, in particular to a method for degrading organic dye wastewater by catalyzing photo-assisted carbide slag ferrosilicon, which comprises the following steps: separation and pretreatment of carbide slag ferrosilicon: treating the dry carbide slag to obtain ferrosilicon particles with magnetic characteristics, and then grinding the ferrosilicon particles to 20-100 mu m to obtain ferrosilicon powder; treating organic dye wastewater: firstly, adjusting the pH value of the organic dye wastewater to 3-9, then adding persulfate and the ferrosilicon powder obtained in the step (1) into the organic dye wastewater, assisting with illumination radiation, stirring and reacting until the solution is clear, and then degrading the organic dye in the wastewater. The ferrosilicon material used in the invention is derived from dry carbide slag, realizes the reutilization of tailings resources, conforms to the concept of 'treating waste by waste', can efficiently treat organic dye wastewater, and has simple process flow. In addition, the system can adapt to acidic, alkaline and neutral wastewater environments, namely the pH adaptation range is wide.
Description
Technical Field
The invention relates to the technical field of water treatment and solid waste treatment, in particular to a method for degrading organic dye wastewater by catalyzing carbide slag ferrosilicon through photo-assisted treatment.
Background
In recent years, with the rapid development of chemical industries such as printing and dyeing, textile, coating and the like, the annual production amount of dyes in China is gradually rising. However, about 10% to 20% of the dye is discharged as waste water during the production and use, and if a large amount of untreated dye waste water is directly discharged to the water body, it causes serious damage to the ecological environment. Most organic dyes have the characteristics of high chromaticity and stable chemical properties, so that the direct discharge of the wastewater can influence the growth of aquatic organisms for a long time. The dye wastewater with higher concentration also has stronger biotoxicity, and the discharge of the dye wastewater into a water body can pollute the ecological system of the whole water area, thereby forming great threat to the health of human beings and other organisms.
The current common methods for treating dye wastewater in industry include adsorption, flocculation precipitation, advanced oxidation, biological methods, etc. The advanced oxidation technology has attracted much attention in recent years due to its advantages of high treatment efficiency, simple process, wide application range, etc., and especially the advanced oxidation technology based on persulfate has made great research progress. This type of technique initially utilized homogeneous metal ions to activate persulfates to produce strongly oxidizing sulfate radicals (SO)4-and hydroxyl radicals (. OH), thereby degrading macromolecular organic contaminants in water. Since such a homogeneous system has a large chemical consumption and is liable to cause secondary pollution, heterogeneous metal activators have been developed and utilized. The most commonly used heterogeneous activators at present are zero-valent iron and other iron-based compounds, and although the activators have the advantages of strong activity, low toxicity and easy separation and recovery, the activators still have the problems of poor catalytic stability and high iron dissolution rate, and the application and development of iron-based materials in the field of water treatment are limited to a certain extent.
The carbide slag is solid waste slag produced in the industrial production of acetylene gas, and the main component of the carbide slag is calcium hydroxide, and in addition, the carbide slag also contains a small amount of ferrosilicon substances, and the content of the ferrosilicon substances is about 1% -3%. At present, the treatment method of the dry-method carbide slag is mainly applied to producing building materials such as cement, but in the application approach, the ferrosilicon particles do not play a great role, but can cause adverse effect on the production of the cement, and finally waste of ferrosilicon resources is caused. Therefore, the separation and high-value application of the carbide slag ferrosilicon are important subjects in the field of solid waste treatment.
Ferrosilicon, as an iron-based material with reducibility, theoretically has the feasibility of becoming a metal catalyst in advanced oxidation technology. In summary, if a method can be provided to apply the carbide slag ferrosilicon to the persulfate-based advanced oxidation technology, the method has important significance for the treatment of the carbide slag and the treatment of the dye wastewater.
Disclosure of Invention
The invention aims to provide a method for degrading organic dye wastewater by photo-assisted carbide slag ferrosilicon catalysis, which simultaneously realizes the utilization of the carbide slag ferrosilicon and the efficient treatment of the dye wastewater, and has the advantages of simple process, wide pH application range, stable catalysis effect, low iron dissolution degree and easy recycling.
The working principle of the invention is as follows: in the ferrosilicon/persulfate system, because ferrosilicon granule has reducibility, its surface can be slowly oxidized by persulfate and release a small amount of ferrous ion to activation persulfate or hydrogen persulfate ion produces the free radical, and illumination radiation itself also can play the effect of activation persulfate in addition. Therefore, in the method, the persulfate can be subjected to the coactivation of the ferrosilicon particles and the external illumination to continuously generate a large amount of SO4And OH free radical to realize the efficient decolorizing and eliminating of organic dye in water.
The scheme adopted by the invention for realizing the purpose is as follows: a method for degrading organic dye wastewater by photo-assisted carbide slag ferrosilicon catalysis comprises the following steps:
(1) separation and pretreatment of carbide slag ferrosilicon: treating the dry carbide slag to obtain ferrosilicon particles with magnetic characteristics, and then grinding the ferrosilicon particles to 20-100 mu m to obtain ferrosilicon powder;
(2) treating organic dye wastewater: firstly, adjusting the pH value of the organic dye wastewater to 3-9, then adding persulfate and the ferrosilicon powder obtained in the step (1) into the organic dye wastewater, assisting with illumination radiation, stirring and reacting until the solution is clear, and then degrading the organic dye in the wastewater.
Preferably, in the step (1), the mass percentage of the calcium element in the obtained ferrosilicon powder is not more than 3%.
The ferrosilicon powder prepared by using dry-process carbide slag as a raw material generally comprises the following elements, by mass, 70% to 85% of iron, 10% to 25% of silicon and 3% of calcium.
Preferably, in the step (2), the organic dye is a cationic dye or an azo-type organic dye, and the concentration of the organic dye wastewater treated is 0.5-50 mg/L.
Typical cationic dyes include methylene blue, rose bengal B, etc., and azo-type organic dyes include methyl orange, congo red, etc.
Preferably, in the step (2), the persulfate is at least one of sodium persulfate, potassium persulfate, ammonium persulfate and oxone.
Preferably, in the step (2), the wavelength range of the illumination radiation is 320-780 nm.
Preferably, in the step (2), the dosage of the ferrosilicon powder is 0.40-0.60g/L, and the dosage of the persulfate is 0.25-0.75 g/L.
Preferably, in the step (2), the stirring speed is 200-.
The invention has the following advantages and beneficial effects:
1. the ferrosilicon material used in the invention is derived from dry carbide slag, and artificial synthesis preparation is not needed, thus being beneficial to reducing the process cost. In addition, the method provides a novel application approach of the carbide slag ferrosilicon for wastewater treatment, realizes the reutilization of tailings resources, and conforms to the concept of treating wastes with wastes.
2. The ferrosilicon/persulfate system disclosed by the invention can be used for efficiently treating organic dye wastewater, and the process flow is simple. In addition, the system can adapt to acidic, alkaline and neutral wastewater environments, namely the pH adaptation range is wide. In addition, the ferrosilicon particles have good catalytic stability when being used as an activator of persulfate, and the concentration of dissolved iron ions is low, so that the secondary pollution of excessive metal ions is avoided.
3. The carbide slag ferrosilicon used in the invention has obvious magnetic characteristics, which is beneficial to the separation and recycling of the ferrosilicon after wastewater treatment, thereby further reducing the treatment cost of dye wastewater and reducing environmental pollution.
Drawings
FIG. 1 is a graph showing the degradation effect of irradiation assisted carbide slag ferrosilicon in degrading organic dyes in examples 1 to 4 of the present invention;
FIG. 2 is a graph showing the results of the cyclic degradation experiment using the carbide slag ferrosilicon in example 5 of the present invention.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1
Firstly, dry-method carbide slag produced by a certain plant is subjected to air separation and magnetic separation two-stage separation treatment, wherein a cyclone separator and a dry-type magnetic separator are respectively adopted by air separation and magnetic separation equipment. The concentrate obtained after sorting is ferrosilicon particles, and then the ferrosilicon particles are ground to the particle size of 20-100 mu m by a vibration mill for later use. The main elements of the ferrosilicon sample are as follows by X-ray fluorescence spectrum test: iron 72.1%, silicon 20.7%, and calcium 2.5%.
This example takes 100mL of a 20mg/L methylene blue solution and adds sulfuric acid to it to adjust the pH of the solution to 6.0. Then PMS and ferrosilicon powder are added simultaneously under the illumination radiation with the output power of 40W and the wavelength of 320-780nm, the dosage of the PMS and the ferrosilicon powder is 0.25g/L and 0.5g/L respectively, and the mixture is stirred and reacted for 45min at the speed of 300 r/min. During the reaction, the methylene blue concentration of the solution is detected by using an ultraviolet-visible spectrophotometer.
The degradation effect of methylene blue in this example is shown in fig. 1, and it can be seen that the degradation rate of methylene blue at 45min of the reaction of this group is 98.0%, and the solution is in a colorless and clear state, indicating the complete removal of methylene blue.
Example 2
The preparation method and the element composition of the carbide slag ferrosilicon in the embodiment are the same as those in embodiment 1, 100mL of methylene blue solution with the concentration of 20mg/L is taken, sulfuric acid is added to the methylene blue solution to adjust the pH value of the solution to 3.0, then PMS and ferrosilicon powder are simultaneously added under the illumination radiation with the output power of 50W and the wavelength of 320-780nm, at the moment, the dosage of the PMS and the ferrosilicon powder is 0.5g/L, and the stirring reaction is carried out for 45min at 200 r/min. The methylene blue concentration of the solution was also measured using an ultraviolet-visible spectrophotometer.
The degradation effect of methylene blue in the example is shown in fig. 1, and it can be shown that the degradation rate of methylene blue in the group can reach 99.6% when the group reacts for 45min, which also indicates that the organic dye is completely removed.
Example 3
The preparation method and the element composition of the carbide slag ferrosilicon in the embodiment are the same as those in embodiment 1, 100mL of methylene blue solution with the concentration of 20mg/L is taken, sodium hydroxide is added to adjust the pH value of the solution to 9.0, then PMS and ferrosilicon powder are simultaneously added under the illumination radiation with the output power of 60W and the wavelength of 320-780nm, the dosage of the PMS and the dosage of the ferrosilicon powder are respectively 0.5g/L and 0.6g/L, and the stirring reaction is carried out for 45min at 300 r/min. The methylene blue concentration of the solution was also measured using an ultraviolet-visible spectrophotometer.
The degradation effect of methylene blue in this example is shown in fig. 1, and it can be seen that the degradation rate of methylene blue reaches 99.9% when the reaction is carried out for 45min under the condition.
The combination of examples 1-3 shows that the system has a wide pH adaptation range, and thus can be applied to acidic, alkaline and neutral wastewater environments.
Example 4
The preparation method and the element composition of the carbide slag ferrosilicon in the embodiment are the same as those in embodiment 1, 100mL of methyl orange solution with the concentration of 20mg/L is taken, sulfuric acid is added to the methyl orange solution to adjust the pH value of the solution to 4.0, then PMS and ferrosilicon powder are simultaneously added under the illumination radiation with the output power of 40W and the wavelength of 320-780nm, the dosage of the PMS and the dosage of the ferrosilicon powder are respectively 0.25g/L and 0.5g/L, and the mixture is stirred and reacted for 45min at 500 r/min. And detecting the concentration of methyl orange in the solution by using an ultraviolet-visible spectrophotometer.
The degradation effect of methyl orange in this example is shown in fig. 1, and it can be seen that the degradation rate of methyl orange reaches 98.7% when the reaction is carried out for 45min under the condition. This example illustrates that the process is equally applicable to azo-type dyes such as methyl orange.
Example 5
Step 1) in this example was substantially the same as in example 1, and 100mL of a methylene blue solution having a concentration of 20mg/L was taken, and sulfuric acid was added thereto to adjust the pH of the solution to 6.0, and then the amounts of PMS and ferrosilicon powder were each 0.5g/L, and the other parameters were the same as in example 1. And after the first degradation process is finished, carrying out suction filtration and recovery, washing by deionized water, drying at 60 ℃ for 30-60min, then carrying out degradation on new methylene blue solution again, carrying out five-cycle degradation experiments totally, and keeping the parameters of each experiment consistent. After the completion of each reaction cycle, the iron ion concentration of each filtrate was measured by an atomic absorption spectrometer.
The experimental results of this example are shown in fig. 2, and it can be seen that the degradation rate of methylene blue in each experiment is more than 99%, and in addition, the iron ion concentration of the solution after the reaction is completed is always kept at about 2.0mg/L, and the corresponding iron dissolution rate is calculated to be within the range of 0.3% -0.7%. The experimental result of figure 2 shows that the ferrosilicon particles have good catalytic stability and proper iron dissolution degree in the reaction system, which is beneficial to the repeated cyclic utilization of the substance, thereby reducing the process cost.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (7)
1. A method for degrading organic dye wastewater by photo-assisted carbide slag ferrosilicon catalysis is characterized by comprising the following steps:
(1) separation and pretreatment of carbide slag ferrosilicon: treating the dry carbide slag to obtain ferrosilicon particles with magnetic characteristics, and then grinding the ferrosilicon particles to 20-100 mu m to obtain ferrosilicon powder;
(2) treating organic dye wastewater: firstly, adjusting the pH value of the organic dye wastewater to 3-9, then adding persulfate and the ferrosilicon powder obtained in the step (1) into the organic dye wastewater, assisting with illumination radiation, stirring and reacting until the solution is clear, and then degrading the organic dye in the wastewater.
2. The method for degrading organic dye wastewater by using the photo-assisted carbide slag ferrosilicon as claimed in claim 1, which is characterized in that: and (2) in the step (1), the mass percent of the calcium element in the obtained ferrosilicon powder is not more than 3%.
3. The method for degrading organic dye wastewater by using the photo-assisted carbide slag ferrosilicon as claimed in claim 1, which is characterized in that: in the step (2), the organic dye is a cationic dye or an azo organic dye, and the concentration of the treated organic dye wastewater is 0.5-50 mg/L.
4. The method for degrading organic dye wastewater by using the photo-assisted carbide slag ferrosilicon as claimed in claim 1, which is characterized in that: in the step (2), the persulfate is at least one of sodium persulfate, potassium persulfate, ammonium persulfate and potassium hydrogen persulfate.
5. The method for degrading organic dye wastewater by using the photo-assisted carbide slag ferrosilicon as claimed in claim 1, which is characterized in that: in the step (2), the wavelength range of the illumination radiation is 320-780 nm.
6. The method for degrading organic dye wastewater by using the photo-assisted carbide slag ferrosilicon as claimed in claim 1, which is characterized in that: in the step (2), the dosage of the ferrosilicon powder is 0.40-0.60g/L, and the dosage of the persulfate is 0.25-0.75 g/L.
7. The method for degrading organic dye wastewater by using the photo-assisted carbide slag ferrosilicon as claimed in claim 1, which is characterized in that: in the step (2), the stirring speed is 200-500 r/min.
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2021
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